Resinous condensation products and process of making them



' Patented JaiulO, 1933:

I E L Boy 1;. KIENLE,

No Drawing.

The present invention relates to artificial:

resins of the condensed ester type and com prises an improved resinouscomposition which contains in a combined state oxidiz-J' .to llustrate,the manner "of carrying out my 55 5 able, unsaturated fatty. acid, .forexample,

suchacids as may be derived fromdrying oils.

i [It isthe object of my invention to produce;

resins of the polyhydric alcohol-polyba'sic acid class which can befully hardened or set at ordinary room temperatures,'that 1s, withoutbaking, which shall have greaterv hard- 7 ness and. elasticity and ingeneralhave more advantageous physical properties .forin dustrialpurposes than alkyd resins which have been produced heretofore. .Alkydresins, as'isknown, include the complexes re'- sulting from the reactionof-polyhydric alcohols and 'resinifying ca'rb'oxyl-ic organic acidssuch' as the polybasicacids or-"their anhydridesa 1 Arsem Ills. Pa e1,098,776 bf June2',"

1914 describes the preparation of' alkyd resins from a polyhydricalcohol, such as.

glycerine, and a cyclic polybasic acid, such as phthalic acid, togetherwith an aliphatic acid. Included among the aliphatic acids are fattyacids, such as stearic and oleic acids. These fatty acids are of thenon-drying type,that is, they are not hardened by oxidation.

I have discovered that when an aromatic or cyclic polybasic acid, suchas phthalic acid, is associated with an unsaturated, ox-

idizable acid, namely. an acid derivedfrom a dryin'goil, such,-forexample, as eleostearic, lmohc, or llnolenlc ac1d,- such acids having.

, more than one double bond in the molecule, that then anew form ofresinous material 40 is produced which diflersjin many import:

ant respects from the resin-containing anondrying fatty acid.For-example,- such a resin is soluble at ordinary temperatures in.adrying oil. The resin containing such acid is convertible by contactwith the air 'at ordinary temperatures to a hard, toughfstateQ Whenapplied in solution on metal or otherfoundation material a; tough,flexible I and" drying oil. 1 y

The resins made in accordance with my tenac'eously adherent film isformed upon evaporation of the solvent and air drying.

or sortminoramnnn'wirortx, AssIGuon -ro GENERAL ELECTRIC com-1mm,A'CQRPOBATION on NEW YORK ansmous eonnnusa'rron rnonucrs AND rnoonss orMAKING 'rnnm Application medjanuar 2a, 1927. Serial No, 1s4,ee2.

All these properties render this resin valuable as an ingredient invarnishes or other protective coatings. i The following specificexamples are given invention and the character of the products derivedtherefrom,

. F irstewampla-a- About 92 parts by weight of glyce'rine and 296 partsby weight of phth'alicanhydride' are heated with the to temperaturegradually rising. At about 160 C. a clear, straw-coloredsolutionisproduced. The-temperature is gradually increased to about 200 C. tocause a reaction to proceed, I water vapor and'some anhydride. beinggiven off. At this pointan additional quantity of phthalic anhydride maybe 'addcd,,*say

about 74: parts by Weight, and also about 140 parts 'of one or.morefatty acids derived from a drying joil, such-as China wood, linseed, orperillaloil. Heatingis continued at a temperature within therange'of"190 G. to 210 C. until froth-ing and the giving off of vaporsceases and a clear liquid is formed. Instead of the mixed acids derivedfrom a 7 drying oil, which include alsoas minorconstituentsnon-oxidizablei fatty-acids, I may use one or more oxidizable,unsaturated acids, such as eleostearic, linolic orllinolenic acidsunassociated with other fatty acids.

Second ea'a-mpZe.The cyclic or aromatic acid-maybe mixed with thealiphatic acid and reaction the-n may-be carried out in one stage theaddition of glycerine. By weight,

ut 370 parts of phthalic a-nhydride and about 1 10 parts'of thefattya'cids derived from one of the drying oils are melted by heating toabout-160 C. About92 parts of'glycerine then are added and thetemperature is raised to about 200C. until resinification occurs. Iprefer to heat the mixture until a resin formed which stringsout atabout 180 r pswhen allowed to fall in A resin prepared by either methodis more flexible and tougher than a resin derived from glycerine andphthalic anhydride alone, unassociate'd with the acid derivedfrom abenzol, coal tar oil, acetone oil, butyl acetate,

butyl alcohol, ethyl lactate, glycol diacetate,

'gl col, lycol derivatives such as the monoetli l ether, be l acetate,phthalateesters suc as diethyl giithalate, tr1acetin.

When such resin dissolved in a suitable solvent of the types lied. as avarnis a tough, tenaceously erent film is r uced uponevaporation of thesolvent an aird 'ng of the resin. Upon air drying the resin omes notonly hardened but also non-fusible and'insoluble in ordina organicsolvents. Such a film is articu arly advantageous for coating metalscause of its adherence.

The resin also may be utilized in massive or bulk form, for example, bycasting the fused resin into suitable mold to roduce slabs, sheets oringots, which may heat hardened, if desired' The resin also may be usedin conjunction withvvarious fillers for the preparation of moldedproducts, or as a cement or as a binder for laminated materials, or asan impregnant for porous materials.

The resins made in accordance with my invention are miscible directly bysimple heatingwith drying oils, such as linseed oil, Chinawood oil,perilla oil, or blown fish oil. Such solutions are usefulas a varnishfor coating metals, wood or other articles.

It will be obvious that the resins made in accordance with my inventionwill yield on saponification the alcohols and acids from which they'areformed.

Obviously the appended claims, except where otherwise specificallylimited, are in- -tended to cover the products and processes whetherobtained or practiced by multi-stage operations as illustrated inExample 1, or

b a one-stage operation as illustrated in Example 2 hereinabove.

5 What I claim as new and desire tosecure by Letters Patent of theUnited States, is,-

1. A resinous composition constituted by the reaction product of apolyhydric alcohol,

a polybasic aromatic acid and air drying fatty acid.

2. A resinous composition constituted by s the reaction product of apolyhydric alcohol, a polybasic aromatic acid and mixed fattyacids'derived from China wood oil.

3. A resinous composition constituted by the reaction product of aolyhydric alcohol, a polybasic aromatic ac d and fatty acids derivedfrom linseed oil.

4. A resinous composition constituted by the condensation product ofglycerine, phthalic anhydride and an oxidizable unsaturated fatty acidhaving more than one'double bond in the molecule.

5. A resin constituted by the reaction product of a polyhydric alcohol,a polybasic mentioned above is a mixed fatty acids de- 7 A resinousmaterial com rising the re- I action product of a polyhy ric a ohol, aresinifying carbox lic organic acid and a fatty acidderived rom an oilhaving drying properties.

8. A resinous composition produced by the reaction of about 92 parts oflycerine, about 370 parts of phthahc anhyd rideand about 140 parts ofmixed fatt acid derived from a drying oil, said arts ing by weight.

9. A. fusible so uble polyhydric alcohol polybasic acid resin which iscapable of being converted to the infusible, insoluble state byoxidation and which contains an acidradical of a drying oil in chemicalcombination.

10. A fusible soluble polyhydric alcohol-polyb'asic acid resin which iscapable of being converted to the soluble state by oxidization, andwhich contains a radical of an air drying fatty acid in chemicalcombination.

11. A fusible soluble polyhydric alcoholpolybasic acidresin which iscapable of being converted to the infusible insoluble state byoxidization, and which contains a fatty acid radical of linseed oil .in:chemical combination.

12. A fusible soluble polyhydric alcoholpolybasic acid resin which iscapable of being converted to the infusible insoluble state byoxidization, and which contains a radical of an oxidizable unsaturatedfatty acid having,

more than one double bond in the molecule in chemical combination.

13. The process of making an air drying fusible, soluble, resinouscomposition which consistsin reacting upon a polyhydric alcohol with apolybasic organic acid and ,fatty acid derived from a'drying oil.

14. The process of making an air (1 in fusible soluble resinouscomposition whic consists in reacting upon ajpolyhydric alco-' hol witha pol ybasic organic acid and air drying fatty acid.

.15. The process of making an air d in fusible soluble resinouscomposition w ic consists in reacting upon a polyhydric alcohol with apolybasic organic acid and fatty acids derived from linseed oil. 16. Theprocess of making an air d ing" fusible soluble resinous composition wich consists inreacting upon a polyhydric alcohol with a polyba'sicorganic acid and an oxidizable unsaturated fatty acid having more thanone double bond in the molecule.

17. The process of making a varnish resin which consists in reacting amixture of glycinfusible in- 99 erine, hthalic anhydride and fatty acidderived rom a drying oil.

18. The process of making a resin which comprises reacting a mixture ofglycerine,

' phthalic anhydride and air drying fatty acid.

1 discontinuing the heating when resinification has occurred.

22. A product soluble in various mixed organic solvents and comprising aresinous reaction product of a polyhydric alcohol a resinifyingcarboxylic organic acid an a dryding oil acid more unsaturated thanoleic aci 23. A product soluble in various mixed organic solventscomprising resinified glycerides of a resinifying carboxylic organicacid and an oily fatty acid comprising an acid more unsaturated thanoleic acid.

24. The process of making a resinous product soluble in various mixedorganic solvents which comprises heating to reaction temperature a masscomprising a polyhydric. alcohol, a resinifying carboxylic organic acidand a drying oil acid more unsaturated than oleic aci 25. The process ofmakin a resinous product soluble in various mixe' organic solvents whichcomprises heating to reaction temperature a mass comprising g1 cerol, aresinifying carboxylic organic aci and an oily fatty acid moreunsaturated'than oleic acid.

26. A new composition of matter havin the property of hardening byabsorption 0 oxygen at atmospheric temperature and comprising apolyhydric alcohol-polybasic acid ester containing a fatty acid radicalof an oil having drying properties.

27. The process of producing a synthetic resin which comprises heatingto reaction temperature a reaction mass containing glycerol, phthalicacid and linseed oil acid.

28. The process of producing a synthetic resin which comprises heatingto reaction temperature a reaction mass containing a poliyhydricalcohol, a giol basic organic acid an acids obtainable y ing oil.

29. The recess of producing a synthetic resin whic comprises heating toreaction temperature a reaction mass containing a acid derived fromdrying oil and ydrolyzing a drying essentially a mixed ester in whichthe alcohol radical is that of a polyhydric alcohol and the acidradicals are those of a.

polybasic organic acid and acids obtainable by hydrolyzing adrying oil.

32. A new composition of matter comprising essentially a mixed ester ofglycerol, phthalic acid and linseed oil acid.

33. A coating composition comprising a mixed ester and a solventtherefor, said mixed ester having as the alcohol component a polyhydricalco 01, and as the acid components a olybasic organic acid and acidsobtainable y the hydrolysis of drying oil.

34. A coating composition comprising a mixed ester of glycerin and asolvent therefor, said mixed ester having as the acid componentsphthalic acid and acids obtainable by the hydrolysis of drying oil.

35. A coating composition comprising a mixed ester of glycerin and asolvent therefor, said mixedester having as the acid components phthalicacid and acids obtainable by the hydrolysis of China wood oil.

36. A coating composition comprising a mixed ester of glycerin and asolvent therefor, said mixed ester having as the acid componentsphthalic acid and acids obtainable by the hydrolysis of China wood oiland linseed oil.

37. A resinous product which on saponification yields a polyhydricalcohol, a resinibasic organic acid, an drying oil acids comprisingChina wood oil acids.

41. A resinous product which on saponification yields glycerol, phthalicacid, and dryin oil acids. I

n witness whereof I have hereunto set my hand this'27th day of January,1927.

ROY H. KIENLE.

fyingcarboxylic organic acid, and a drying

